Magnetic materials with enhanced perpendicular anisotropy energy density for stt-ram

ABSTRACT

A mechanism is provided for a spin torque transfer random access memory device. A reference layer is disposed on a seed layer. A tunnel barrier is disposed on the reference layer. A free layer is disposed on the tunnel barrier. A cap layer is disposed on the free layer. The free layer includes a magnetic layer and a metal oxide layer, in which the magnetic layer is disposed on the tunnel barrier and the metal oxide layer is disposed on the magnetic layer. A metal material used in the metal oxide layer includes at least one of Ti, Ta, Ru, Hf, Al, La, and any combination thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 13/911,602, entitled “MAGNETIC MATERIALS WITH ENHANCEDPERPENDICULAR ANISOTROPY ENERGY DENSITY FOR STT-RAM”, filed on Jun. 6,2013, which is incorporated herein by reference in its entirety.

BACKGROUND

The present invention relates generally to spin torque transfer, andmore specifically, to materials in and configurations for a spin torquetransfer random access memory device.

Spin transfer torque is an effect in which the orientation of a magneticlayer in a magnetic tunnel junction or spin valve can be modified usinga spin-polarized current. Charge carriers (such as electrons) have aproperty known as spin which is a small quantity of angular momentumintrinsic to the carrier. An electrical current is generally unpolarized(consisting of 50% spin-up and 50% spin-down electrons). A spinpolarized current is one with more electrons of either spin. By passinga current through a thick magnetic layer, one can produce aspin-polarized current. If a spin-polarized current is directed into amagnetic layer, angular momentum can be transferred to the magneticlayer, changing its magnetic orientation. This can be used to flip theorientation of the magnet.

BRIEF SUMMARY

According to an exemplary embodiment, a spin torque transfer randomaccess memory device is provided. The device includes a reference layerdisposed on a seed layer, a tunnel barrier disposed on the referencelayer, a free layer disposed on the tunnel barrier, and a cap layerdisposed on the free layer. The free layer includes a magnetic layer anda metal oxide layer, where the magnetic layer is disposed on the tunnelbarrier and the metal oxide layer is disposed on the magnetic layer. Ametal material used in the metal oxide layer includes at least one ofMg, Ti, Ta, Ru, Hf, Al, La, and any combination thereof.

According to another exemplary embodiment, a spin torque transfer randomaccess memory device is provided. The device includes a reference layerdisposed on a seed layer, a tunnel barrier disposed on the referencelayer, a free layer disposed on the tunnel barrier, and a cap layerdisposed on the free layer. The free layer includes a first magneticlayer disposed on the tunnel barrier, a spacer layer disposed on thefirst magnetic layer, a second magnetic layer disposed on the spacerlayer, and a metal oxide layer disposed on the second magnetic layer.The metal material used in the metal oxide layer includes at least oneof Mg, Ti, Ta, Ru, Hf, Al, La, and any combination thereof.

According to another exemplary embodiment, a method of forming a spintorque transfer random access memory device is provided. The methodincludes disposing a reference layer on a seed layer, disposing a tunnelbarrier on the reference layer, disposing a free layer on the tunnelbarrier, and disposing a cap layer on the free layer. The free layer maybe formed by disposing a first magnetic layer on the tunnel barrier,disposing a spacer layer on the first magnetic layer, disposing a secondmagnetic layer on the spacer layer, and disposing a metal oxide layer onthe second magnetic layer. Alternatively, the free layer may be formedby disposing the first magnetic layer on the tunnel barrier anddisposing the metal oxide layer on the first magnetic layer. The metalmaterial used in the metal oxide layer includes at least one of Mg, Ti,Ta, Ru, Hf, La, and any combination thereof.

Additional features and advantages are realized through the techniquesof the present invention. Other embodiments and aspects of the inventionare described in detail herein and are considered a part of the claimedinvention. For a better understanding of the invention with theadvantages and the features, refer to the description and to thedrawings.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

The subject matter which is regarded as the invention is particularlypointed out and distinctly claimed in the claims at the conclusion ofthe specification. The forgoing and other features, and advantages ofthe invention are apparent from the following detailed description takenin conjunction with the accompanying drawings in which:

FIG. 1A illustrates a cross-sectional view of a spin torque transferrandom access memory (STT-RAM) device according to an embodiment.

FIG. 1B illustrates a cross-sectional view of the STT-RAM device with anexemplary structure for the free magnetic layer according to anembodiment.

FIG. 1C illustrates a cross-sectional view of the STT-RAM device with anexemplary structure for the free magnetic layer according to anotherembodiment.

FIG. 2 is a chart of M_(s)tH_(k) versus RA comparison according to anembodiment.

FIG. 3 illustrates a method of forming a spin torque transfer randomaccess memory device according to an embodiment.

DETAILED DESCRIPTION

Embodiments disclose a new class of cap materials which can enhance theperpendicular anisotropy of a CoFeB layer significantly withoutsacrificing junction resistance area product (RA) and tunnelmagnetoresistance (TMR).

A CoFeB layer with perpendicular anisotropy has been identified as oneof the most promising materials for the free layer in STT-RAM devices.Compared to other candidate materials, CoFeB has a few distinctadvantages including low damping for lower write voltage and goodstructure match with an MgO tunnel barrier for high TMR. TMR is amagnetoresistive effect that occurs in a magnetic tunnel junction (MTJ),which is a component consisting of two ferromagnets separated by a thininsulator. If the insulating layer is thin enough (typically a fewnanometers), electrons can tunnel from one ferromagnet into the other.

However, when the CoFeB layer (i.e., free layer) is sandwiched betweenthe tunnel barrier and a Ta cap (layer), the energy density(M_(s)tH_(k)) of this material (CoFeB layer) is not particularly high.Since the energy density is directly related to the thermal activationenergy of the patterned STT-RAM device, a low energy density materialwill not meet the retention requirement in small STT-RAM devices, thusaffecting the scalability of this material (CoFeB layer). M_(s) is thesaturation magnetization of the free layer material, t is the thicknessof the free layer, and H_(k) is the perpendicular anisotropy field ofthe free layer. The thermal activation energy barrier of a patterneddevice=M_(s)t·H_(k)·A, where A is the area of the patterned device, whenthe device size is small. M_(s)tH_(k) product is referred to as energydensity. For a given device size, the higher the M_(s)tH_(k) product,the higher the thermal activation energy barrier which translates tobetter retention.

Embodiments disclose free layer materials and structures that have highperpendicular magnetic anisotropy energy density. Perpendicular magneticanisotropy energy density refers to the product of free layer saturationmagnetization M_(s), free layer thickness t, and perpendicularanisotropy field H_(k).

There have been reports on a CoFeB layer sandwiched by two MgO tunnelbarriers with enhanced energy density. However, in that case, theresistance area product (RA) is increased (because of the existence oftwo tunnel barriers and the resistance adds up). Accordingly, the TMRwill be deteriorated. Note that there is a delicate balance betweenperpendicular magnetic anisotropy (PMA) energy density and junction RAin this material system. By choosing the right cap materials andoxidation condition, the PMA energy density can be largely improvedwithout affecting the junction RA. In a patterned device, the junctionresistance across the tunnel barrier=RA (resistance area product)/areaA.

In embodiments, the cap materials that enhance CoFeB PMA energy densityinclude Mg oxide, Ti oxide, Mg/Ti oxide, and Mg/Ta oxide. In this case,the oxides were made by depositing metal layers first and then oxidizingthe metal layers by natural or radical oxidation. In oxide caps, themetal layer thickness is between 1 A to 10 A. Both the PMA energydensity and junction RA depend on the thickness and detailed oxidationcondition of the metal layers.

Magnetic anisotropy is the directional dependence of a material'smagnetic properties. In the absence of an applied magnetic field, amagnetically isotropic material has no preferential direction for itsmagnetic moment, while a magnetically anisotropic material will alignits moment with one of the easy axes (as discussed herein perpendicularmagnetic anisotropy (PMA) is aligned perpendicularly). An easy axis isan energetically favorable direction of spontaneous magnetization thatis determined by the sources of magnetic anisotropy.

According to embodiments, it was also found that when the single CoFeBlayer is replaced by a trilayer structure (as shown in FIG. 1B), thejunction RA can be lowered. This trilayer structure includes two CoFeBlayers separated by a spacer layer. The spacer layer can be Ta or Ti,with a thickness between 0.5 A to 5 A.

Now turning to the figures, FIG. 1A illustrates a cross-sectional viewof a spin torque transfer random access memory (STT-RAM) device 100utilizing magnetic materials with perpendicular magnetic anisotropyaccording to an embodiment. The device structure of the STT-RAM device100 includes a magnetic tunnel junction (MTJ) 70. The magnetic tunneljunction 70 has a reference magnetic layer 20, a tunnel barrier 30 onthe reference magnetic layer 20, and a free magnetic layer 40 on thetunnel barrier 30. The reference magnetic layer 20 is on a seed layer10. The seed layer 10 can be different materials depending on the exactreference magnetic layer 20 and to grow the reference magnetic layer 20.A cap layer 50 is disposed on the free magnetic layer 40. The referencemagnetic layer 20 and the free magnetic layer 40 sandwich the tunnelbarrier 30 in between. The tunnel barrier 30 is a thin insulator.

The free magnetic layer 40 is shown with double arrows to illustratethat spin torque current (or spin polarized current) via voltage source75 can flip the magnetic orientation of the free magnetic layer 40 to upor down as desired. The reference magnetic layer 20 is shown with an uparrow to illustrate a magnetic orientation to the up direction. To writethe STT-RAM device 100, the voltage source 75 applies voltage and a spintorque current can flip the magnetic orientation of the free magneticlayer 40 as desired. When the magnetic orientations of the free magneticlayer 40 and the reference magnetic layer 20 are parallel (i.e.,pointing in the same direction), the resistance of the MTJ 70 is low(e.g., representing logic 1). When the magnetic orientations of the freemagnetic layer 40 and the reference magnetic layer 20 are antiparallel(i.e., pointing in opposite directions), the resistance of the MTJ 70 ishigh (e.g., representing a logic 0).

FIG. 1B illustrates the STT-RAM device 100 with an exemplary structureof the free magnetic layer 40 according to an embodiment. In FIG. 1B,the free magnetic layer 40 is composed of a first magnetic layer 210, aspacer layer 220, and a second magnetic layer 230. The first magneticlayer 210 is made of at least one of the following materials: Fe, CoFe,CoFeB, CoPt, FePt, CoPd, FePd, and/or any combination thereof. Thesecond magnetic layer 230 is made of at least one of the followingmaterials: Fe, CoFe, CoFeB, CoPt, FePt, CoPd, FePd, and/or anycombination thereof. The thickness of the first magnetic layer 210ranges from 5 angstroms (Å) to 20 angstroms. The thickness of the secondmagnetic layer 230 ranges from 5 Å to 20 Å.

The spacer layer 220 is at least one of Ta, Ti, TiN, TaN, TaMg, TiMgand/or any combination thereof. The spacer layer 220 has a thicknessranging from 0.5 Å to 10 Å. The first magnetic layer 210 and the secondmagnetic layer 230 are ferromagnetically coupled through the spacerlayer 220. Accordingly, the first magnetic layer 210 and the secondmagnetic layer 230 are configured to maintain the same magneticorientation via the spacer layer 220. When the voltage source 75 (notshown in FIGS. 1B and 1C for the sake conciseness) generates the spintorque current (spin polarized current) as understood by one skilled inthe art, the magnetic orientations (maintained in the same directionwith respect to one another) of the first magnetic layer 210 and thesecond magnetic layer 230 (forming the free magnetic layer 40) are bothflipped in the same direction according to the angular momentum of thespin torque current. Accordingly, based on the ferromagnetically coupledfirst and second magnetic layers 210 and 230 (i.e., free magnetic layer40) being parallel to the reference magnetic layer 20, the resistance islow and the logic state is 1. On the other hand, based on theferromagnetically coupled first and second magnetic layers 210 and 230(i.e., free magnetic layer 40) being antiparallel to the referencemagnetic layer 20, the resistance is high and the logic state is 0.

Now, further discussion is provided regarding the metal oxide layer 240.In the first oxidation example, the metal oxide layer 240 is made bydepositing metal layers first (for example metal layers of Mg and Ti)and then oxidizing the metal layers by an oxidation process. Theoxidation process to oxidize the metal layers may include naturaloxidation, or radical oxidation as understood by one skilled in the art.

In the second oxidation example, the metal oxide layer 240 is made bydepositing metal layers (for example, metal layers of Mg and Ti) first,oxidizing the metal layers by an oxidation process, and then depositinganother metal layer (for example a metal layer of Mg) after theoxidation process. The oxidation process to oxidize the metal layers mayinclude natural oxidation, or radical oxidation as understood by oneskilled in the art.

In the first and second oxidation examples for making the metal oxidelayer 240, the metal layer material may include at least one of Mg, Ti,Ta, Ru, Hf, La, Al and any combination thereof. The metal layers used inmetal oxide layer 240 have thicknessess between 1 Å to 20 Å.

The cap layer 50 is composed of at least one of Ru, Pd, Pt, Ta, TiN, andany combination thereof. The thickness of the cap layer 50 ranges from 2Å to 40 Å (or more). The choice of this cap layer 50 has a significantimpact on both free layer perpendicular magnetic anisotropy and junctionRA.

FIG. 1C illustrates the STT-RAM device 100 with an exemplary structureof the free magnetic layer 40 according to an embodiment. In FIG. 1C,the free magnetic layer 40 is composed of a magnetic layer 215 and themetal oxide layer 240. In this case, the metal oxide layer 240 isdisposed on the magnetic layer 215, and the magnetic layer 215 isdisposed on the tunnel barrier 30.

The magnetic layer 215 (of the free magnetic layer 40) is composed of atleast one of the following materials: Fe, CoFe, CoFeB, CoPt, FePt, CoPd,FePd, and any combination thereof. The magnetic layer 215 has athickness ranging from 10 Å to 30 Å. As noted above, the first andsecond oxidation examples may be utilized for making the metal oxidelayer 240. In the first oxidation example, the metal oxide layer 240 ismade by depositing metal layers first and then oxidizing the metallayers by an oxidation process. In the second oxidation example, themetal oxide layer 240 is made by depositing metal layers first,oxidizing the metal layers by an oxidation process, and then depositinganother metal layer after the oxidation process. The metal layermaterial of the metal oxide layer 240 is at least one of Mg, Ti, Ta, Ru,Hf, Al and La. The metal layers used in metal oxide layer 240 havethicknesses between 1 Å to 20 Å.

FIG. 2 is a chart 200 of the magnetic property of one particular exampleaccording to an embodiment. In this example, the STT-RAM device 100sample contains a seed layer 10, a tunnel barrier 30, and a freemagnetic layer 40. The free magnetic layer 40 includes the firstmagnetic layer 210 made of CoFeB, the space layer 220 made of Ta, thesecond magnetic layer 230 made of CoFeB, the metal oxide layer 240 madeof a Mei oxide layer stack, and the cap layer 50 made of Ru. The Mg|Timetal oxide layer 240 is made by depositing a metal layer of Mg,depositing a metal layer of Ti (on the metal layer of Mg), and thenoxidizing the Mg|Ti layers by an oxidation process.

The vertical axis of the chart 200 shows the perpendicular magneticanisotropy energy density M_(s)tH_(k) measured on sheet films. TheM_(s)tH_(k) is in the unit of erg/cm², where erg is the unit of energyin the centimeter-gram-second (CGS) system of units. H_(k) is theperpendicular magnetic anisotropy field. M_(s) is saturationmagnetization of the free layer, and t is the thickness of the freelayer. The horizontal axis of the chart 200 shows the resistance areaproduct (RA) in unit of ohm·μm²(Ω·μm²), measured on sheet films.

In FIG. 2, the diamonds are the properties of a free layer with oxidecap, while the dot is from a similar free layer with a metal Ta cap. Byadjusting the metal layer thickness and oxidation conditions, theM_(s)tH_(k) product can be improved by 70-80% while keeping the RA moreor less constant.

FIG. 3 illustrates a method 300 of forming a spin torque transfer randomaccess memory device 100 according to an embodiment.

The reference magnetic layer 20 is disposed on (and/or grown from) theseed layer 10 at block 302. The tunnel barrier 30 is disposed on thereference magnetic layer 20 at block 304. The free magnetic layer 40 isdisposed on the tunnel barrier 30 306. The cap layer 50 is disposed onthe free magnetic layer 40 at block 308.

Disposing the free magnetic layer 40 include one of the following:

With reference to FIG. 1B, making/forming the free magnetic layer 40includes disposing a first magnetic layer 210 on the tunnel barrier 30,disposing a spacer layer 220 on the first magnetic layer 210, disposinga second magnetic layer 230 on the spacer layer 220, and disposing ametal oxide layer 240 on the second magnetic layer 230 at block 310.

With reference to FIG. 1C, making/forming the free magnetic layer 40includes disposing a magnetic layer 215 on the tunnel barrier anddisposing the metal oxide layer 240 on the magnetic layer 215 at block312. The metal oxide material of the metal oxide layer 240 includes atleast one of Mg, Ti, Ta, Ru, Hf, Al, La, and any combination thereof.

In one case, the metal oxide material of the metal oxide layer 240further includes Mg. In another case, the metal oxide material of themetal oxide layer 240 excludes and is free of Mg.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the invention. Asused herein, the singular forms “a”, “an” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises”and/or “comprising,” when used in this specification, specify thepresence of stated features, integers, steps, operations, elements,and/or components, but do not preclude the presence or addition of oneor more other features, integers, steps, operations, element components,and/or groups thereof.

The corresponding structures, materials, acts, and equivalents of allmeans or step plus function elements in the claims below are intended toinclude any structure, material, or act for performing the function incombination with other claimed elements as specifically claimed. Thedescription of the present invention has been presented for purposes ofillustration and description, but is not intended to be exhaustive orlimited to the invention in the form disclosed. Many modifications andvariations will be apparent to those of ordinary skill in the artwithout departing from the scope and spirit of the invention. Theembodiment was chosen and described in order to best explain theprinciples of the invention and the practical application, and to enableothers of ordinary skill in the art to understand the invention forvarious embodiments with various modifications as are suited to theparticular use contemplated.

The diagrams depicted herein are just one example. There may be manyvariations to this diagram or the steps (or operations) describedtherein without departing from the spirit of the invention. Forinstance, the steps may be performed in a differing order or steps maybe added, deleted or modified. All of these variations are considered apart of the claimed invention.

While the preferred embodiment to the invention had been described, itwill be understood that those skilled in the art, both now and in thefuture, may make various improvements and enhancements which fall withinthe scope of the claims which follow. These claims should be construedto maintain the proper protection for the invention first described.

What is claimed is:
 1. A method of forming a spin torque transfer randomaccess memory device, the method comprising: disposing a reference layeron a seed layer; disposing a tunnel barrier on the reference layer;disposing a free layer on the tunnel barrier; and disposing a cap layeron the free layer; wherein disposing the free layer includes one of:disposing a first magnetic layer on the tunnel barrier, disposing aspacer layer on the first magnetic layer, disposing a second magneticlayer on the spacer layer, and disposing a metal oxide layer on thesecond magnetic layer; or disposing the first magnetic layer on thetunnel barrier and disposing the metal oxide layer on the first magneticlayer; wherein the metal material used in the metal oxide layer includesat least one of Mg, Ti, Ta, Ru, Hf, La, and any combination thereof. 2.The method of claim 1, wherein the first magnetic layer includes atleast one of Fe, CoFe, CoFeB, CoPt, FePt, CoPd, FePd, and anycombination thereof;
 3. The method of claim 1, wherein the secondmagnetic layer includes at least one of Fe, CoFe, CoFeB, CoPt, FePt,CoPd, FePd, and any combination thereof.
 4. The method of claim 1,further comprising oxidizing the metal oxide material by depositingmetal layers and oxidizing the metal layers by an oxidation process. 5.The method of claim 1, further comprising oxidizing the metal oxidematerial by depositing metal layers, oxidizing the metal layers by anoxidation process, and depositing another metal layer after theoxidation process.
 6. The method of claim 1, wherein the first magneticlayer has a thickness ranging from 5 angstroms to 20 angstroms; andwherein the second magnetic layer has a thickness ranging from 5angstroms to 20 angstroms.
 7. The method of claim 1, wherein the caplayer includes at least one of Ru, Pd, Pt, Ta, TiN, and any combinationthereof.
 8. The method of claim 1, wherein the cap layer has a thicknessranging from 2 angstroms to 40 angstroms.
 9. The method of claim 1,wherein the spacer layer includes at least one of Ta, Ti, TiN, TaN,TaMg, TiMg, and any combination thereof.
 10. The method of claim 1,wherein the spacer layer has a thickness ranging from 0.5 angstrom to 10angstroms.